Polyolefinic succinimide polyamine alkyl acetoacetate adducts as dispersants in lubricating oil compositions

ABSTRACT

This invention is to a lubricating or fuel oil composition containing polyolefinic succinimide polyamine alkyl acetoacetate adducts of the general formula: ##STR1## wherein Z 1  and Z 3  are moities of the formula: ##STR2## Z 2  is a moiety of the formula: ##STR3## wherein R 2 , R 3  and R 4  are alkylene of from 1 to 6 carbon atoms, m is an integer of from 1 to 5, each A&#39; is H, A and the moiety: ##STR4## wherein A&#34; is H or A, R 3  is as defined above, R 6  is alkylene of from 1 to 6 carbon atoms, T 1  and T 2  are ##STR5## wherein B&#39; is substituted or unsubstituted alkyl or aryl-containing group, n 1 , n 2 , n 3  and n 4  are from 0 to 10 their sum being from 3 to 10, R 1  and R 5  are an olefin polymer, and A comprises a tautomeric substituent of the formula: ##STR6## wherein R 10  is substituted or unsubstituted alkyl or aryl containing groups. 
     The adduct additives are especially useful in concentrates, lubricating oil or fuel oil compositions as dispersants. The formulations have excellent coild flow properties compared to similar formulations not containing the inventive adduct.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is related to the following applications, all filed oneven date herewith: Ser. No. 51,276 filed May 18, 1987 "PolyolefinicSuccinimide Polyamine Alkyl Acetoacetate Adducts"; Ser. No. 51,275 filedMay 18, 1987 "Polyolefinic Succinimide Polyamine Alkyl Acetoacetate andSubstituted Acetate Adducts as Additives in Lubricating OilCompositions"; Ser. No. 51,146 filed May 18, 1987, "PolyolefinicSuccinimide polyamine Alkyl Acetoacetate Adduct Dispersants."

FIELD OF THE INVENTION

This invention is to lubricating oil and concentrate compositionscontaining polyolefinic succinimide polyamine alkyl acetoacetate adductdispersants of the general formula: ##STR7## wherein Z¹ and Z³ are thesame or different and are moieties of the formula: ##STR8## Z² is amoiety of the formula: ##STR9## wherein R², R³ and R⁴ are the same ordifferent and are alkylene of from 1 to 6 carbon atoms, m is an integerof from 1 to 5, each A' is independently selected from the groupconsisting of H, A and the moiety: ##STR10## wherein A" is H or A, R³ isas defined above, R⁶ is alkylene of from 1 to 6 carbon atoms, T¹ and T²are the same or different and each comprises a member selected from thegroup consisting of moieties of the formula: ##STR11## wherein B' issubstituted or unsubstituted alkyl or aryl-containing group, n¹ is aninteger of 0 to 10, n² is an integer of 0 to 10, n³ is an integer offrom 0 to 10, n⁴ is an integer of from 0 to 10, with the provisos thatthe sum of n¹, n², n³ and n⁴ is from 3 to 10 and the sum of n¹, n³ andn⁴ is at least 1, wherein R¹ and R⁵ are independently an olefin polymerhaving a number average molecular weight (M_(n)) between about 650 and3,500, and wherein A comprises a tautomeric substituent of the formula:##STR12## wherein R¹⁰ is substituted or unsubstituted alkyl or arylcontaining groups, with the proviso that at least one of the A' or A"groups comprises said substituted acetyl or said tautomeric substituent,wherein at least about 95% of T¹ and T² groups in adduct dispersantscomprise said succinimide moiety of the formula: ##STR13## wherein R⁵ isas defined above.

The adduct additives are especially useful in lubricating oil or fueloil compositions or in the additive concentrates used in making up thosecompositions. They are excellent dispersants when used in thosecompositions and provide superior low temperature fluid flow propertiesto those compositions.

BACKGROUND OF THE INVENTION

Polyalkene substituted carboxylic acids are widely known and used asadditives in lubricating oils.

Illustrations of such materials are shown in numerous patents.

U.S. Pat. No. 3,215,707 discloses the reaction of chlorine with amixture of polyolefin, having molecular weights up to about 50,000, andmaleic anhydride.

U.S. Pat. No. 3,927,041 discloses the reaction of 300 to 3,000 molecularweight polybutene with a dicarboxylic acid or anhydride to formmaterials which can be used per se, or as esters, amides, imides,amidines, or the like in petroleum products.

U.S. Pat. No. 4,062,786 provides an example (No. 13) of polyisobutylenesuccinic anhydride having a molecular weight of about 1300, asaponification number of about 100, and about 1.25 succinic anhydrideunits per polyisobutylene unit.

U.S. Pat. No. 4,123,373 shows a similar material having a molecularweight of about 1400, a saponification number of 80, and about 1.07succinic anhydride units per polyisobutylene unit.

U.S. Pat. No. 4,234,435 also shows polyalkene substituted dicarboxylicacids derived from polyalkenes having an average molecular weight of1300 to 5000.

Polyalkenyl succinic anhydrides have also been reacted with polyaminesto form materials suitable for use as dispersants in lubricating oils.

U.S. Pat. Nos. 4,113,639 and 4,116,876 provides an example of alkenylsuccinic anhydride in which the molecular weight of the alkenyl unit isabout 1300a saponification number of 103, and about 1.3 succinicanhydride units per hydrocarbon molecule. The material is then reactedwith a polyamine and boric acid (U.S. Pat. No. 4,113,63 or with an aminoalcohol and boric acid (U.S. Pat. No. 4,118,876).

U.S. Pat. No. 4,548,724 teaches a lubricating oil additive comprisingthe reaction product of a polycarboxylic acid, e.g., 1,3,6-hexanecarboxylic acid, with a polyisobutylene succinimide and a polyamine.

U.S. Pat. No. 4,579,675 relates to the reaction products of polyalkylenesuccinimides (derived from polyethylene-polyamines) and 1,3-dicarbonylcompounds. However, the reaction temperatures are such that the productsare materials known as N-substituted enaminones. Therefore,polyisobutenyl succinimide, derived from polyisobutenyl succinicanhydride and diethylene triamine, was reacted with ethyl acetoacetateat 110° C. to form the corresponding N-substituted enaminone. Thereaction is carried out in the presence of an alkylsulfonic acid tofavor the formation of what appears to be a kinetically preferredproduct, the enaminone. The adduct of the present invention furthermorehas, as its by-product, an alcohol or mercaptan rather than theby-product water of the U.S. Pat. No. 4,579,675. The enaminone reactionproducts are said to have detergent/dispersant properties when includedin a lubricating oil composition.

No known disclosure suggests either the products disclosed herein or theuse of these inventive adducts as dispersants.

SUMMARY OF THE INVENTION

This invention is to hydrocarbon containing oleaginous compositionspolyolefinic succinimide polyamine alkyl acetoacetate adducts of thegeneral formula: ##STR14## wherein Z¹ and Z³ are the same or differentand are moieties of the formula: ##STR15## Z² is a moiety of theformula: ##STR16## wherein R², R³ and R⁴ are the same or different andare alkylene of from 1 to 6 carbon atoms, m is an integer of from 1 to5, each A' is independently selected from the group consisting of H, Aand the moiety: ##STR17## wherein A" is H or A, R³ is as defined above,R⁶ is alkylene of from 1 to 6 carbon atoms, T¹ and T² are the same ordifferent and each comprises a member selected from the group consistingof moieties of the formula: ##STR18## wherein B' is substituted orunsubstituted alkyl or aryl-containing group, n¹ is an integer of 0 to10, n² is an integer of 0 to 10, n³ is an integer of from 0 to 10, n⁴ isan integer of from 0 to 10, with the provisos that the sum of n¹, n², n³and n⁴ is form 3 to 10 and the sum of n¹, n³ and n⁴ is at least 1,wherein R¹ and R⁵ are independently an olefin polymer having a numberaverage molecular weight (M_(n)) between about 650 and 3,500, andwherein A comprises a tautomeric substituent of the formula: ##STR19##wherein R¹⁰ is substituted or unsubstituted alkyl or aryl containinggroups, with the proviso that at least one of the A' or A" groupscomprises said substituted acetyl or said tautomeric substituent,wherein at least about 95% of T¹ and T² groups in adduct dispersantscomprise said succinimide moiety of the formula: ##STR20## wherein R⁵ isas defined above.

Also included in the invention are compositions containing mixtures ofadducts fitting the above description, particularly adducts in which themixtures contain adducts in which the T¹ and/or T² substituents are boththe amide and the succinimide. However, the mixtures must contain asubstantial majority of the bis-succinimide form.

The compositions containing these adducts are useful as lubricating orfuel compositions. The compositions may also contain other (orauxiliary) high molecular weight dispersants, high total base numberdetergents and antiwear agents or antioxidants. The adducts providesuperb dispersancy in the compositions and, when used in lubricating oilcompositions, also give the added benefit of superior cold flowproperties.

DETAILED DESCRIPTION OF THE INVENTION

Lubricating oil compositions, e.g., automatic transmission fluids, heavyduty oils suitable for gasoline and diesel engines, etc., can beprepared using the compositions of this invention. Universal typecrankcase oils, those in which the same lubricating oil composition isused for either gasoline or diesel engines, may also be prepared. Theselubricating oil formulations conventionally contain several differenttypes of additives that supply the characteristics that are required forthe particular use. Among these additives are included viscosity indeximprovers, antioxidants, corrosion inhibitors, detergents, dispersants,pour point depressants, anitwear agents, etc.

The dispersant used in lubricating oil compositions have the primaryfunction of dispersing particulate materials formed in the engine andkeeping those materials in dispersion. As a rule of thumb, thedispersants having the higher molecular weight have higher efficiency inmaintaining particulates in dispersion than those with lower molecularweight. Higher molecular weight, however, often causes increasedvisosity in the finished formulation. This result may be a benefit inthat high temperature lubricating properties are maintained. Increasedviscosity may, however, cause increased pumping losses in an engine andresult in lower gas mileage. Increased viscosity at low temperature mayalso cause substantial problems in attempting to start engines duringthe winter. Compositions containing the inventive adduct show excellentdispersant capabilities and yet provide superior cold start operation.

In the preparation of lubricating oil formulations, it is commonpractice to introduce the additives in the form of a concentrate (forinstance, as an "ad pack") containing 10 to 80 weight percent, e.g., 20to 80 weight precent, active ingredients in a solvent. The solvent maybe hydrocarbon oil, e.g., a mineral lubricating oil, or other suitablematerial. In forming finished lubricants, such as crankcase motor oils,these concentrates, in turn, may be diluted with 3 to 100, e.g., 5 to40, parts by weight of lubricating oil per part by weight of theadditive package. One uses concentrates, of course, to make the handlingof the various constituent materials less difficult as well as tofacilitate solution or dispersion of those materials in the final blend.The inventive adducts may be used in concentrates containing otheradditives suitable for formulating finished lubricating oilformulations.

THE COMPOSITIONS

Oleaginous compositions made according to this invention generally willcontain at least:

a. a lubricating or fuel oil, and, p1 b. polyolefinic succinimidepolyamine alkyl acetoacetate dispersant adducts of this invention.

The dispersants of this invention are oil-soluble, dissolvable in oilwith the aid of a suitable solvent, or are stably dispersible materials.Oil-soluble, dissolvable, or stably dispersible as that terminology isused herein does not necessarily indicate that the materials aresoluble, dissolvable, miscible, or capable of being suspended in oil inall proportions. It does mean, however, that the dispersant additives,for instance, are soluble or stably dispersible in oil to an extentsufficient to exert their intended effect in the environmment in whichthe oil is employed. Moreover, the additional incorporation of otheradditives may also permit incorporation of higher levels of a particulardispersant, if desired.

Accordingly, while any effective amount of the dispersant additives canbe incorporated into the lubricating oil composition, it is contemplatedthat such effective amount be sufficient to provide said lube oilcomposition with an amount of the additives of typically from about 0.10to about 15 e.g., 0.1 to 10, and preferably from about 0.1 to about 7wt. %, based on the weight of said composition.

The dispersant additives of the present invention can be incorporatedinto the lubricating oil in any convenient way. Thus, they can be addeddirectly to the oil by dispersing, or dissolving the same in the oil atthe desired level of concentration typically with the aid of a suitablesolvent such as toluence, or tetrahydrofuran. Such blending can occur atroom temperature or elevated temperatures. Alternatively, the dispersantadditives may be blended with a suitable oil-soluble solvent and baseoil to form a concentrate, and then blending the concentrate withlubricating oil base stock to obtain the final formulation. Concentrateswill typically contain from about 20 to 60 wt. %, by weight dispersantadditive, and typically from about 80 about 20%, preferably from about60 to about 20% by weight base oil, based on concentrate weight.

The dispersant of this invention can be employed as additiveconcentrates comprising concentrated solutions or dispersions of thedispersant (in concentrate amounts hereinabove described), together withone or more of said other additives (said concentrate when constitutingan additive mixture being referred to herein as an additive-package)whereby several additives can be added simultaneously to the base oil toform the lubricating oil composition. Dissolution of the additiveconcentrate into the lubricating oil may be facilitated by solvents andby mixing accompanied with mild heating, but this is not essential. Theconcentrate or additive-package will typically be formulated to containthe dispersant additive and optional additional additives in properamounts to provide the desired concentration in the final formulationwhen the additive-package is combined with a predetermined amount ofbase lubricant. Thus, the dispersant of the present invention can beadded to small amounts of base oil or other compatible solvents alongwith other desirable additives to form additive-packages containingactive ingredients in collective amounts of typically from about 2.5 toabout 90%, and preferably from about 5 to about 75%, and most preferablyfrom about 8 to about 50% by weight additives in the appropriateproportions with the remainder being base oil.

The final formulations may employ typically about 10 wt. % of theadditive-package with the remainder being base oil.

All of said weight percent expressed herein are based on activeingredient (A.I.) content of the additive, and/or upon the total weightof any additive-package, or formulation which will be the sum of theA.I. weight of each additive plus the weight of the total oil ordiluent.

Depending upon the use to which the compositions are ultimately placed,the compositions may also include auxiliary dispersants, detergents/rustinhibitors, antiwear additives, antioxidants, friction modifiers, pourpoint depressants, viscosity index improvers and the like.

The compositions of this mixture contain at least the inventivedispersant in an amount effective to provide its dispersant functions.

Compositions may be blended containing the following additives inamounts effective to provide their normal attendant functions. Theseadditive effective amounts are illustrated as follows:

    ______________________________________                                                          Wt. % a.i.                                                                              Weight % a.i.                                     Additive          (Broad)   (Preferred)                                       ______________________________________                                        Viscosity Modifier                                                                              0.01-12   0.1-16                                            Corrosion Inhibitor                                                                             0.01-5    0.01-1.5                                          Oxidation Inhibitor                                                                             0.01-5    0.01-1.5                                          Dispersants (Total)                                                                             0.1-20    0.1-14                                            Pour Point Depressant                                                                           0.01-5    0.01-1.5                                          Antifoaming Agents                                                                              0.001-3   0.001-0.15                                        Antiwear Agents   0.001-5   0.001-1.5                                         Friction Modifiers                                                                              0.01-5    0.01-1.5                                          Detergent/Rust Inhibitors                                                                       0.01-20   0.01-1.5                                          Mineral Oil Base  Balance   Balance                                           ______________________________________                                    

When the compositions of the invention are used in the form oflubricating oil compositions, such as automotive crankcase lubricatingoil compositions, a major amount of a lubricating oil may be included inthe composition. Broadly, the composition may contain about 85 to about99.99 weight percent of a lubricating oil. Preferably, about 93 about99.8 weight percent of the lubricating oil. The term "lubricating oil"is intended to include not only hydrocarbon oils derived from protroleumbut also synthetic oils such as alkyl esters of dicarboxylic acids,polyglycols and alcohols, polyalphaolefins, alkyl benzenes, organicesters of phosphoric acids, polysilicone oils, etc.

When the compositions of this invention are provided in the form ofconcentrates, with or without other additives, a minor amount, e.g., upto about 50 percent by weight, of a solvent, mineral or synthetic oilmay be included to enchance the handling properties of the concentrate.

When the compositions are used as normally liquid petroleum fuels suchas gasoline, and middle distillates boiling from about 66° to 430° C.,including kerosene, diesel fuels, home heating fuel oil, jet fuels,etc., a concentration of the additive in the fuel in the range of 0.001to 0.5, preferably about 0.001 to 0.1 weight percent, based on theweight of the total composition, will usually be employed.

DISPERSANTS

As has been noted before, this invention is to compositions containing,as dispersants, polyolefinic succinimide polyamine alkyl acetoacetateadducts of the general formula (I): ##STR21## wherein Z¹ and Z³ are thesame or different and are moieties of the formula: ##STR22## Z² is amoiety of the formula: ##STR23## wherein R², R³ and R⁴ are the same ordifferent and are alkylene of from 1 to 6 carbon atoms, m is an integerof from 1 to 5, each A' is independently selected from the groupconsisting of H, A and the moiety: ##STR24## wherein A" is H or A, R³ isas defined above, R⁶ is alkylene of from 1 to 6 carbon atoms, T¹ and T²are the same or different and each comprises a member selected from thegroup consisting of moieties of the formula: ##STR25## wherein B' issubstituted or unsubstituted alkyl or aryl-containing group, n¹ is aninteger of 0 to 10, n² is an integer of 0 to 10, n³ is an integer offrom 0 to 10, n⁴ is an integer of from 0 to 10, with provisos that thesum of n¹, n², n³ and n⁴ is from 3 to 10 and the sum of n¹, n³ and n⁴ isat least 1, wherein R¹ and R⁵ are independently an olefin polymer havinga number average molecular weight (M_(n)) between about 650 and 3,500,and wherein A comprises a tautomeric substituent of the formula (Ia):##STR26## wherein R¹⁰ is substituted or unsubstituted alkyl or arylcontaining groups, with the proviso that at least one of the A' or A"groups comprises saide tautomeric substituent, wherein at least about95% of T¹ and T² groups in adduct dispersants comprise said succinimidemoiety of the formula (Ib): ##STR27## wherein R⁵ is as defined above.

R¹ and R⁵ groups may be the same or different and may be H or olefinicpolymeric residues produced from C₂ to C₁₀ monoolefins. Such olefins maybe ethylene, propylene, butylene, isobutylene, pentene, octene-1,styrene, etc. The polymers may be homopolymers such as polyisobutylene,as well as copolymers of two or more of such olefins such as copolymersof: ethylene and propylene; butylene and isobutylene; propylene andisobutylene; etc., other copolymers are those in which a minor molaramount of the copolymer monomers, e.g., 1 to 10 mole percent, is a C₄ toC₁₈ diolefin, e.g., a copolymer of isobutylene and butadiene; or acopolymer of ethylene, propylene and 1,4-hexadiene; etc.

The olefin polymer may be completely saturated as in the example of anethylene-propylene copolymer made by Ziegler-Natta synthesis usinghydrogen as a moderator to control molecular weight.

The olefinic polymer will usually have number average molecular weightswithin the range of about 650 and about 3500, more usually between about800 and about 3000. Particularly useful olefin polymers have numberaverage molecular weights within the range of about 900 and about 2,300with approximately one double bond per polymer chain. An especiallyuseful starting material is polyisobutylene.

The R², R⁴ and R⁶ groups are alkyl linkages having from 1 to 6 carbonatoms. The preferred linkage is a C₂ to C₄ link (e.g., --CH₂ --, --C₂ H₄--, --C₃ H₆ --, and --C₄ H₈ --). Most preferred is an ethylene linkage.

Preferably, when n² is zero, the value of n¹ is from 1 to 5, n³ is from0 to 5, and n⁴ is from 0 to 5, and the sum of integers n¹, n³ and n⁴ ispreferably from 2 to 10, and more preferably from 3 to 7. When n² is notzero, preferably each A¹ is independently selected form H or A, and thevalue of n¹ is from 1 to 5, n² is from 1 to 3, n³ is from 0 to 5, andthe total of integers n¹, n² and n³ is from 2 to 10, and more preferablyfrom 3 to 7.

The R¹⁰ group may be a substituted or unsubstituted alkyl oraryl-containing group but desirably is a lower alkyl having 1 to 4carbon atoms and preferably is a methyl group.

As noted above, T¹ and T² may be either secondary or tertiary amidegroups of the formula: ##STR28## or polyolefin substitutedsuccinimide-containing groups of the formula (Ib): ##STR29##

Mixtures of adducts fitting the above description comprise adductswherein at least about 95%, more preferably at least about 99%, and mostpreferably at least about 99.5% of the T¹ and T² groups comprise theabove polyolefin substituted succinimide-containing groups (Ib).

Exemplary of adducts of this invention derived from cyclic alkylenepolyamines are adducts of the formula I wherein n¹, n² and n³ are eachintegers of 1 to 3, R² and R⁴ are each C₂ to C₄ alkylene, A' is A, n⁴ isan integer of 1 to 3, R³ is --CH₂ CH₂ --, T¹ is ##STR30## --NH(A), A isthe tautomeric substituent of the formula Ia wherein R¹⁰ is C₁ to C₂alkyl, and wherein R¹ and R⁵ are the same or different and arepolyalklene (especially, polyisobutylene or polybutylene) having M_(n)of from 1,500 to 3,000. Illustrative such adducts are those of theformula (III): ##STR31## wherein R¹, R⁵ and A are as defined in theprior sentence.

Exemplary of adducts of this invention derived from straight andbranched chain polyalkylene polyamines are adducts of formula I whereinn² is zero, n¹ and n³ are each integers of from 1 to 3, R² is C₂ to C₄alkylene, each A' is: ##STR32## R³ is --CH₂ CH₂ --, n⁴ is an integer of1 to 3, R⁶ is C₂ to C₄ alkylene, T¹ and T² are as defined in formula I,A is the tautomeric substituent of formula (Ib) wherin R¹⁰ is C₁ to C₂alkyl, and R¹ and R⁵ are the same or different and are polyalkylenehaving M_(n) of from 1,500 to 3,000. Exemplary of adducts derived fromsuch branched chain polyalkylene polyamines are adducts of the formula(IV): ##STR33## wherein A' is: ##STR34## wherein R¹, A and R⁵ are asdefined in the prior sentence. Exemplary of adducts derived fromstraight chain polyalkylene polyamines are adducts of formula (IV)wherein A' is H or A.

Adducts of this invention derived from straight chain polyalkylenepolyamines are preferred.

Exemplary of preferred compatibilizer adducts of this invention are:##STR35## wherein A' is A, and wherein R¹, R², R³, and T¹ as defined inTable I below:

                                      TABLE I                                     __________________________________________________________________________                              R.sup.10 of                                         R.sup.1    x R.sup.2                                                                             R.sup.3                                                                              Each A(1)                                                                           T.sup.1                                       __________________________________________________________________________    Derived from:                                                                 polyisobutylene                                                                          5 C.sub.2 H.sub.4                                                                     CH.sub.2 CH.sub.2                                                                    CH.sub.3                                                                            NH(A),                                        --M.sub.n = 700                 R.sup.10 = CH.sub.3                           polyisobutylene                                                                          3 CH.sub.2                                                                            C.sub.3 H.sub.6                                                                      C.sub.2 H.sub.5                                                                     NH(A),                                        --M.sub.n = 2,200               R.sup.10 = CH.sub.3                           polybutene 4 C.sub.5 H.sub.10                                                                    C.sub.4 H.sub.8                                                                      H     NH(A).sub.2,                                  --M.sub.n = 1,200               R.sup.10 = H                                  polybutene 2 C.sub.2 H.sub.4                                                                     C.sub.2 H.sub.4                                                                      C.sub.2 H.sub.5                                                                     NH(A).sub.2,                                  --M.sub.n = 4,000               R.sup.10 = C.sub.2 H.sub. 5                   polypentene                                                                              5 C.sub.3 H.sub.6                                                                     C.sub.3 H.sub.6                                                                      C.sub.4 H.sub.9                                                                     N(A).sub.2,                                   --M.sub.n = 1,800               R.sup.10 = C.sub.4 H.sub.9                    ethylene-propylene co-polymer --M.sub.n = 3,000                                          2 C.sub.2 H.sub.4                                                                     C.sub.2 H.sub.4                                                                      CH.sub.3                                                                             ##STR36##                                    polyisobutylene                                                                          2 C.sub.2 H.sub.4                                                                     C.sub.2 H.sub.4                                                                      CH.sub.3                                                                            (2)                                           __________________________________________________________________________     Notes:-                                                                       .sup.(1) Wherein A = the tautomeric substituent of formula Ia.                ##STR37##                                                                

These adducts may be made in a variety of ways. Certain portions of thereaction scheme are believed to be important in producing the describedmolecule. Those steps will be highlighted at appropriate junctures.

The step in this process which produces the adducts of this invention isthe reaction of an alkyl acetoacetate of formula (VI): ##STR38## or thealkyl thioacetate of the formula (VII): ##STR39## (wherein R¹⁰ is asdefined above and R¹⁵ may be H or substituted or unsubstituted alkyl oraryl but is preferably a C₁ to C₆ alkyl) with a long chain polyolefinicdicarboxylic acid which has been aminated with a polyamine, such as thesaturated aliphatic amines, alicyclic diamines, and polyoxyalkylenes offormulae (XIII)-(XVIII) discussed below. Preferred are polyalkylenepolyamines of from 5 to 9 carbon atoms, e.g., tetraethylene pentamine.This reaction should be practiced at a temperature sufficiently high toproduce substantial amounts of the tautomeric keto-enol rather than theenaminone. Generally, temperatures of from 120° to 220° C. will besuitable, with 150° to 180° C. being preferred. Temperatures of at leastabout 150° C. typically meet this goal although proper choice oftemperature depends on many factors, including reactants, concentration,reaction solvent choice, etc. The reaction of the animated polyolefinicdicarboxcylic acid material and the alkyl acetonate and the alkylthioacetate will liberate the corresponding HOR¹⁵ and HSR¹⁵ by-products,respectively. Preferably, such by-products are substantially removed, asby distillation or stripping with an inert gas (such as N₂), prior touse of the adduct as described herein. Such distillation and strippingsteps are conveniently performed at elevated temperature, e.g., at theselected reaction temperature (for example, at 150° C. or higher).

The amount of alkyl aceto-acetate and/or alkyl thioacetate reactantsused can vary widely, and is preferably selected so as to avoidsubstantial excesses of these reactants. Generally, these reactants areused in a reactant:amine nitrogen-equivalent molar ratio of from about0.1 1:1, and preferably from about 0.5 to 1:1, wherein the moles ofamine nitrogen-equivalent is the moles of secondary nitrogens plus twicethe moles of primary nitrogens in the aminated polyolefinic dicarboxylicacid material (e.g,. PIBSA-PAM) which is thus contacted with the alkylacetonate or alkyl thioacetate. The reaction should also be conducted inthe substantial absence of strong acids (e.g., mineral acids, such asHCl, HB₂, H₂ SO₄, H₃ PO₃ and the like, and sulfonic acids, such aspara-toluene sulfonic acids) to avoid the undesired side-reactions anddecrease in yield to the adducts of this invention.

Methods for producing the long chain polyolefinic dicarboxylic acidsubstrate and the subseqeuent amination are known and are discussedbelow in the section discussing Auxiliary Dispersants.

Such long chain polyolefinic dicarboxylic acid substrates can beillustrated by compounds of the formula: ##STR40## wherein R¹ is asdefined above, or the corresponding diacid: ##STR41## wherein R¹ is asdefined above, or mixtures thereof.

Exemplalry of amines employed are members selected from the groupconsisting of compounds of the formula: ##STR42## wherein Z' and Z" arethe same or different and are moieties of the formula: ##STR43## Z" is amoiety of the formula: ##STR44## wherein R², R³ and R⁴ are the same ordifferent and are alkylidene of from 1 to 6 carbon atoms, m is aninteger of from 1 to 5, each D' is independently selected from the groupconsisting of H and the moiety ##STR45## wherein R⁶ is alkylene of from1 to 6 carbon atoms, c¹ is an integer of 0 to 10, c² is an integer of 0to 10, c³ is an integer of from 0 to 10, c⁴ is an integer of from 0 to10, with the provisos that the sum of c¹, c², c³ and c⁴ is from 3 to 10and the sum of c¹, c³ and c⁴ is at least 1.

The resulting animated polyolefinic dicarboxylic acid substratematerials can be generically illustrated by compounds of the formula(X): ##STR46## wherein Z' and Z'" are the same or different and aremoieties of the formula: ##STR47## Z" is a moiety of the formula:##STR48## wherein R², R³ and R⁴ are the same or different and arealkylene of from 1 to 6 carbon atoms, m is an integer of from 1 to 5,each D' is independently selected from the group consisting of H and themoiety: ##STR49## wherein R³ is as defined above, R⁶ is alkylene of from1 to 6 carbon atoms, L¹ and L² are the same or different and eachcomprises a member selected from the group consisting of moieties of theformula: ##STR50## wherein L³ is subsitituted or unsubstituted alkyl oraryl-containing group, c¹ is an integer of from 0 to 10, c² is aninteger of from 0 to 10, c³ is an integer of from 0 to 10, c⁴ is aninteger of from 0 to 10, with the proivisos that the sum of c¹, c², c³and c⁴ is from 3 to 10 and the sum of c¹, c³ and c⁴ is at least one.

The resulting animated polyolefinic dicarboxylic acid substratematerials prepared from polyalkylene polyamines can be illustrated bygeneral formulae: ##STR51## wherein x is an integer of from 1 to 10.

Typically, they will be produced in mixtures of the two.

The polyolefinic dicarboxylic acid substrate material after amination,is then reacted with an alkyl acetoacetate or with an alkyl thioacetateas described above.

An alternative method of synthesizing the inventive adduct is one inwhich, in a first step, the above-noted amine compounds are firstreacted with the listed alkyl acetoacetates or alkyl thioacetate. Theresulting material, in a seconds step, may then be reacted with thepolyolefinic dicarboxylic acid material. The first step may be done bysimply mixing the reactant amines and alkyl acetoacetates at atemperature of from about 120° to 220° C., preferably at least about150° C., more preferably 150° C. to 180° C. to form an amino compoundsubstituted by at least one tautomeric substituent of the formula (Ia):##STR52## wherein R¹⁰ is as defined above.

A neutral diluent such as mineral oil may be used but is not needed. Thesecond step desirably takes place in a neutral diluent such as a mineraloil at a temperature between 100° C. and 230° C. The temperature is notparticularly critical but takes place at a higher rate at the highertemperature range, e.g., at least about 150° C. As in the firstabove-mentioned method, it is preferable to distill and/or use inert gasstripping (e.g., with N₂), at elevated temperatures, to substantiallyremove by-product HOR¹⁵ or HSR¹⁵ from the amine-alkyl acetoacetate (oralkyl thioacetate) reaction mixture, and the reaction should beconducted in the substantial absence of strong acids.

The adducts of this invention may be treated by boration as generallytaught in U.S. Pat. Nos. 3,087,936 and 3,254,024 (which are incorporatedby reference). This is accomplished by treating the adduct with a boroncompound selected from boron oxide, boron halides, boron acids, andesters of boron acids in an amount sufficient to provide from about 0.1to about 20 atomic proportion of boron for each mole of adduct.Desirably those proportions will be from 0.05 to 2.0 weight percent,e.g., 0.05 to 0.7 weight percent, boron based or the total weight of theadduct.

Treating may be carried out by adding from about 0.05 to 4 weightpercent of the boron compound (preferably boric acid) to the adduct andheating while stirring between 135° C. to 190° C. The time of reactionmay be 1 to 5 hours. Nitrogen stripping may be used during or after thereacton.

THE AUXILIARY DISPERSANT

The auxiliary dispersants which may optionally be included in thisinventive composition comprise nitrogen or ester containing dispersantsselected from the group consisting of (i) oil soluble salts, amides,imides, oxazolines and esters, or mixtures thereof, of long chainhydrocarbon substituted mono and dicarboxylic acids or their anhydrides;(ii) long chain aliphatic hydrocarbon having a polyamine attacheddirectly thereto; and (iii) Mannich condensation products formed bycondensing about a molar proportion of a long chain substituted phenolwith about 1 to 2.5 moles of formaldehyde and about 0.5 to 2 moles ofpolyalkylene polyamine; wherein said long chain hydrocarbon group in(i), (ii) and (iii) is a polymer of a C₂ to C₁₀, e.g., C₂ to C₅,monoolefin, said polymer having a number average molecular weight ofabout 300 to 5000.

A(i) The long chain hydrocarbyl substituted mono- or dicarboxylic acidmaterial, i.e. acid, anhydride, or ester, used in the invention includeslong chain hydrocarbon, generally a polyolefin, substituted with anaverage of at least about 0.8, generally from about 1.0 to 2.0,preferably 1.05 to 1.4, more preferably 1.1 to 1.30, per mole ofpolyolefin, of an alpha or beta unsaturated C₄ to C₁₀ dicarboxylic acid,or anhydride or ester thereof, such as fumaric acid, itaconic acid,maleic acid, maleic anhydride, chloromaleic acid, dimethyl fumarate,chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid,cinnamic acid, and mixtures thereof.

The preferred auxiliary dispersants are long chain hydrocarbylsubstituted dicarboxylic acid materials, i.e., acids, anhydrides, oresters. They include a long chain hydrocarbon, generally a polyolefin,which may be substituted with at least 1.05 molecules of an alpha orbeta unsaturated C₄ to C₁₀ dicarboxylic acid, itaconic acid, maleicacid, maleic anhydride, chloromaleic acid, dimethyl fumarate,chloromaleic anhydride, etc. per mole of polyolefin.

Preferred olefin polymers for the reaction with the unsaturateddicarboxylic acids are those polymers made up of a major molar amount ofC₂ to C₁₀, e.g., C₂ to C₅, monoolefin. Such olefins include ethylene,propylene, butylene, isobutylene, pentene, octene-1, styrene, etc. Thepolymers may be homopolymers such as polyisobutylene or copolymers oftwo or more of such olefins. These include copolymers of: ethylene andpropylene; butylene and isobutylene; propylene and isobutylene; etc.Other copolymers include those in which a minor molar amount of thecopolymer monomers, e.g., 1 to 10 mole percent is a C₄ to C₁₈ diolefin,e.g., copolymer of isobutylene and butadiene; or a copolymer ofethylene, propylene and 1.4-hexadiene; etc.

In some cases, the olefin polymer may be completely saturated, forexample an ethylene-propylene copolymer made by a Ziegler-Nattasynthesis using hydrogen as a moderator to control molecular weight.

The olefin polymers will usually have number average molecular weightsabove about 700, and preferably from about 800 to about 5000.Particularly useful olefin polymers have number average molecularweights within the range of about 1200 and about 5000 with approximatelyone double bond per polymer chain. An especially suitable startingmaterial for a dispersant additive in polyisobutylene. The numbermolecular weight for such polymers can be determined by several knowntechniques. A convenient method for such determination is by gelpermeation chromatography (6PC) which additionally provides molecularweight distribution information, see W. W. Yau, J. J. Kirkland and D. D.Bly, "Modern Size Exclusion Liquid Chromatography, " John Wiley andSons, New York, 1979.

Processes for reacting the olefin polymer with the C₄ -C₁₀ unsaturateddicarboxylic acid, anhydride or ester are known in the art. For example,the olefin polymer and the dicarboxylic acid material may be simplyheated together as disclosed in U.S. Pat. Nos. 3,361,673 and 3,401,118to cause a thermal "ene" reaction to take place. Or, the olefin polymercan be first halogenated, for example, chlorinated or brominated toabout 1 to 8, preferably 3 to 7 weight percent chlorine, or bromine,based on the weight of polymer, by passing the chlorine or brominethrough the polyolefin at a temperature of 60° to 250°, e.g., 120° to160° C. for about 0.5 to 10, preferably 1 to 7 hours. The halogenatedpolymer may then be reacted with sufficient unsaturated acid oranhydride at 100° to 250°, usually about 180° to 220° C. for about 0.5to 10 , e.g., 3 to 8 hours. Processes of this general type are taught inU.S. Pat. Nos. 3,087,436; 3,172,892; 3,272,746 and others.

Alternatively, the olefin polymer, and the unsaturated acid material aremixed and heated while adding chlorine to the hot material. Processes ofthis type are disclosed in U.S. Pat. Nos. 3,215,707; 3,231,587;3,912,764; 4,110,349; 4,234,435; and in U.K. Pat. No. 1,440,219.

By the use of halogen, about 65 to 95 weight percent of the polyolefinwill normally react with the dicarboxylic acid material. Thermalreactions, those carried out without the use of halogen or a catalyst,cause only about 50 to 75 weight percent of the polyisobutylene toreact. Chlorination obviously helps to increase the reactivity. Forconvenience, all of the aforesaid functionality ratios of dicarboxylicacid producing units to polyolefin, e.g., 1.0 to 2.0, etc., are basedupon the total amount of polyolefin, that is, the total of both thereacted and unreacted polyolefin, present in the resulting productformed in the aforesaid reactions.

The dicarboxylic acid producing materials can also be further reactedwith amines, alcohols, including polyols, amino-alcohols, etc. to formother useful dispersant additives. Thus, if the acid producing materialis to be further reacted, e.g., neutralized, then generally a majorproportion of at least 50 percent of the acid units up to all the acidunits will be reacted.

Useful amine compound for neutralization of the hydrocarbyl substituteddicarboxylic acid material include mono-and polyamines of about 2 to 60,e.g., 3 to 20, total carbon atoms and about 1 to 12, e.g., 2 to 8nitrogen atoms in the molecule. These amines may be hydrocarbyl aminesor may be hydrocarbyl amines including other groups, e.g., hydroxygroups, alkoxy groups, amide groups, nitriles, imidazoline groups, andthe like. Hydroxy amines with 1 to 6 hydroxy groups, preferably 1 to 3hydroxy groups are particularly useful. Preferred amines are aliphaticsaturated amines, including those of the general formulas: ##STR53##wherein R, R', R" and R'" are independently selected from the groupconsisting of hydrogen; C₁ to C₂₅ straight or branched chain alkylradicals; C₁ to C₁₂ alkoxy C₂ to C₆ alkylene radicals; C₂ to C₁₂alkyl-amino C₂ to C₆ alkylene radicals; and wherein R'" can additionallycomprise a moiety of the formula: ##STR54## wherein R' is as definedabove, and wherein each s and s' can be the same or a different numberof from 2 to 6, preferable 2 to 4; and t and t' can be the same ordifferent and each numbers of from 0 to 10, preferably 2 to 7 with theproviso that the sum of t and t' is not greater than 10. To assure afacile reaction, it is preferred that R, R', R", R'", s, s', t and t' beselected in a manner sufficient to provide the compounds of FormulasXIII and XIV with typically at least one primary or secondary aminegroup, preferably at least two primary or secondary amine groups. Thiscan be achieved by selecting at least one of said R, R', R" or R'"groups of to be hydrogen or by letting t in Formula Ib be at least onewhen R'" is H or when the (XV) moiety possesses a secondary amino group.The most preferred amine of the above formulas are represented byFormula XIV and contain at least two primary amine groups and at leastone, and preferably at least three, secondary amine groups.

Non-limiting examples of suitable amine compounds include:1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane;1,6diaminohexane; polyethylene amines such as diethylene triamine;triethylene tetramine; tetraethylene pentamine; polypropylene aminessuch as 1,2-propylene diamine; di-(1,2-propylene)triamine;di-(1,3-propylene)triamine; N,N-dimethyl-1, -3-diaminopropane;N,N-di-(2-aminoethyl) ethylene diamine;N,N-di(2-hydroxyethyl)-1,3-propylene diamine; 3-dodecyloxypropylamine;N-dodecyl-1,3-propane diamine; tris hydroxymethylaminomethane (THAM);diisopropanol amine; diethanol amine; triethanol amine; mone-, di-, andtri-tallow amines; amino morpholines such as N-(3-aminopropyl)morpholine; and mixtures thereof.

Other useful amine compounds include: alicyclic diamines such as1,4-di(aminomethyl) cyclohexane, and heterocyclic nitrogen compoundssuch as imidazolines, and N-aminoalkyl piperazines of the generalformula (XVI): ##STR55## wherein p1 and p2 are the same or different andare each integers of from 1 to 4, and n', n" and n"' are the same ordifferent and are each integers of from 1 to 3.

Non-limiting examples of such amines include 2-pentadecyl imidazoline;N-(2-aminoethyl) piperazine; etc.

Commercial mixtures of amine compounds may advantageously be used. Forexample, one process for preparing alkylene amines involves the reactionof an alkylene dihalide (such as ethylene dichloride or propylenedichloride) with ammonia, which results in a complex mixture of alkyleneamines wherein pairs of nitrogens are joined by alkylene groups, formingsuch compounds as diethylene triamine, triethylenetetramine,tetraethylene pentamine and isomeric piperazines. Low cost poly(ethyleneamine) compounds averaging about 5 to 7 nitrogen atoms permolecular are available commercially under trade names such as"Polyamine H," "Polyamine 400," "Dow Polyamine E-100," etc.

Useful amines also include polyoxyalkylene polyamines such as those ofthe formulae (XVII):

    (i) NH.sub.2 --alkylene--0--alkylene--.sub.r NH.sub.2      (i)

where "r" has a value of about 3 to 70 and preferably 10 to 35; and theformula (XVIII):

    (ii) R--alkylene--0--alkylene .sub.n NH.sub.2).sub.a       (ii)

where "n" has a value of about 1 to 40 with the provision that the sumof all the n's is from about 3 to about 70 and preferably from about 6to about 35 and R is a polyvalent saturated hydrocarbon radical of up toten carbon atoms wherein the number of substituents on the R group isrepresented by the value of "a", which is a number from 3 to 6. Thealkylene groups in either formula (XVII) or (XVIII) may be straight orbranched chains containing about 2 to 7, and preferably about 2 to 4carbon atoms.

The polyoxyalkylene polyamines above, preferably polyoxyalkylenediamines and polyoxyalkylene triamines, may have average molecularweights ranging from about 200 to about 4000 and preferably from about400 to about 2000. The preferred polyoxyalkylene polyamines include thepolyoxyethylene and polyoxypropylene diamines cular weights ranging fromabout 200 to 2000. The polyoxyalkylene polyamines are commerciallyavailable and may be obtained, for example, from the Jefferson ChemicalCompany, Inc. under the trade name "Jeffamines D-230, D-400, D-1000,D-2000, T-403," etc.

The amine is readily reacted with the dicarboxylic acid material, e.g.,alkenyl succinic anhydride, by heating an oil solution containing 5 to95 weight percent of dicarboxylic acid material to about 100 to 250° C.,preferably 125° to 175° C., generally for 1 to 10, e.g., 2 to 6 hours,until the desired amount of water is removed. The heating is preferablycarried out to favor formation of imides or mixtures of imides andamides, rather than amides and salts. Reaction ratios of dicarboxylicacid material to equivalents of amine as well as the other nucleophilicreactants described herein can vary considerably, depending upon thereactants and type of bonds formed. Generally from 0.1 to 1.0,preferably about 0.2 to 0.6, e.g., 0.4 to 0.6, moles of dicarboxylicacid moiety content (e.g. grafted maleic anhydride content) is used, perequivalent of nucleophilic reactant, e.g. amine. For example, about 0.8mole of a pentamine (having two primary amino groups and 5 equivalentsof nitrogen per molecule) is preferably used to convert into a mixtureof amides and imides, the product formed by reacting one mole of olefinwith sufficient maleic anhydride to add 1.6 moles of succinic anhydridegroups per mole of olefin, i.e. preferably the pentamine is used in anamount sufficient to provide about 0.4 mole (that is 1.6÷[0.8×5] mole)of succinic anhydride moiety per nitrogen equivalent of the amine.

The nitrogen-containing auxiliary dispersant can be further treated byboration as generally taught in U.S. Pat. Nos. 3,087,936 and 3,254,025(the entirety of which is incorporated by reference). This is readilyaccomplished by treating said acyl nitrogen dispersant with a boroncompound selected from the class consisting of boron oxide, boronhalides, boron acids and esters of boron acids in an amount ot providefrom about 0.1 atomic proportion of boron for each mole of said acylatednitrogen composition to about 20 atomic proportions of boron for eachatomic proprtion of nitrogen of said acylated nitrogen composition.Usefully the dispersants of the inventive combination contain from about0.05 to 2.0 weight percent, e.g., 0.05 to 0.7 weight percent, boronbased on the total weight of said borated acyl nitrogen compound. Theboron, which appears to be in the product as dehydrated boric acidpolymer (primarily (HBO₂)₃), is believed to attach to the dispersantimides and diimides as amine salts, e.g., the metaborate salt of saiddiimide.

Treating is readily carried out by adding from about 0.05 to 4, e.g., 1to 3 weight percent (based on the weight of said acyl nitrogen compound)of said boron compound, preferably boric acid which is most usuallyadded as a slurry to said acyl nitrogen compound and heating withstirring at from about 135° C. to 190°, e.g., 140°-170° C., for from 1to 5 hours followed by nitrogen stripping at said temperature ranges.Or, the boron treatment can be carried out by adding boric acid to thehot reaction mixture of the dicarboxylic acid material and amine whileremoving water.

Tris (hydroxymethyl) amino methane (THAM) can be reacted with theaforesaid acid material to form amides, imides or ester type additivesas taught by U.K. 984,409, or to form oxazoline compounds and boratedoxazoline compounds as described, for example, in U.S. Pat. Nos.4,102,798; 4,116,876 and 4,113,639.

The ashless dispersants may also be esters derived from the long chainhydrocarbyl substituted dicarboxylic acid material and from hydroxycompounds such as monohydric an polyhydric alcohols or aromaticcompounds such as phenols and napthols, etc. The polyhydric alcohols arethe most preferred hydroxy compound and preferably contain from 2 toabout 10 hydroxy radicals, for example, ethylene glycol, diethyleneglycol, triethylene glycol, tetraethylene glycol, dipropylene glycol,and other alkylene glycols in which the alkylene radical contains from 2to about 8 carbon atoms. Other useful polyhydric alcohols includeglycerol, mono-oleate of glycerol, monostearate of glycerol, monomethylether of glycerol, pentaerythritol, dipentaerythritol, etc.

The ester dispersant may also be derived from unsaturated alcohols suchas allyl alcohol, cinnamyl alcohol, propargyl alcohol,1-cyclohexane-3-ol, and oleyl alcohol. Still other classes of thealcohols capable of yielding the esters of this invention comprise theether-alcohols and aminoalcohols including, for example, theoxy-alkylene, oxy-arylene-, amino-alkylene-, andamino-arylene-substituted alcohols having one or more oxy-alkylene,amino-alkylene or amino-arylene radicals. They are exemplidied byCellosolve, Carbitol, N,N,N', N'-tetrahydroxy-trimethylene di-amine, andether-alcohols having up to about 150 oxy-alkylene radicals in which thealkylene radical contains from 1 to about 8 carbon atoms.

The ester dispersant may be di-esters of succinic acids or acidicesters, i.e., partially esterified succinic acids; as well as partiallyesterified polyhydric alcohols or phenols, i.e., esters having freealcohols or phenolic hydroxyl radicals. Mixtures of the aboveillustrated esters likewise are contemplated within the scope of thisinvention.

The ester dispersant may be prepared by one of several known methods asillustrated for example in U.S. Pat. No. 3,381,022.

Hydroxyamines which can be reacted with the long chain hydrocarbonsubstituted dicarboxylic acid material mentioned above to formdispersants include 2-amino-1-butanol, 2-amino-2-methyl-1-propanol,p-(beta-hydroxyethyl) -aniline, 2-amino-1-propanol, 3-amino-1propanol,2-amino-2-methyl-1,3-propane-diol, 2-amino-2-ethyl-1,3-propanediol,N-(beta-hydroxy-propyl)-N'-(beta-amino-ethyl)-piperazine,tris(hydroxymethyl) amino-methane (also known astrismethylolaminomethane), 2-amino-1-butanol, ethanolamine,beta-(beta-hydroxyethoxy)-ethylamine, and the like. Mixtures of these orsimilar amines can also be employed.

A very suitable dispersant is one derived from polyisobutylenesubstituted with succinic anhydride groups and reacted with polyethlyeneamines, e.g., tetraethylene pentamine, pentaethylene hexamine,polyoxyethylene and polyoxypropylene amines, e.g., polyoxypropylenediamine, trismethylolaminomethane and pentaerythritol, and combinationsthereof. One preferred dispersant combination involves a combination of(A) polyisobutene substituted with succinic anhydride groups and reactedwith (B) a hydroxy compound, e.g., pentaerythritol, (C) apolyoxy-alkylene polyamine, e.g., polyoxypropylene diamine, and (D) apolyalkylene polyamine, e.g., polyethylene diamine and tetraethylenepentamine using about 0.3 to about 2 moles each of (B) and (D) and about0.3 to about 2 moles of (C) per mole of (A) as described in U.S. Pat.No. 3,804,763. Another preferred dispersant combination involves thecombination of (A) polyisobutenyl succinic anhydride with (B) apolyalkylene polyamine, e.g., tetraethylene pentamine, and (C) apolyhydric alcohol or polyhydroxy-substituted aliphatic primary amine,e.g., pentaerythritol or trismethylolaminomethane as described in U.S.Pat. No. 3,632,511.

A(ii) Also useful as ashless nirtogen-containing dispersant in thisinvention are dispersants wherein a nitrogen containing polyamine isattached directly to the long chain aliphatic hydrocarbon as shown inU.S. Pat. Nos. 3,275,554 and 3,565,804 where the halogen group on thehalogenated hydrocarbon is displaced with various alkylene polyamines.

A(iii) Another class of nitrogen containing dispersants which may beused are those containing Mannich base or Mannich condensation productsas they are known in the art. Such Mannich condensation productsgenerally are prepared by condensing about 1 mole of a high molecularweight hydrocarbyl substituted mono- or polyhydroxy benzene (e.g.,having a number average molecular weight of 1,000 or greater) with about1 to 2.5 moles of formaldehyde or paraformaldehyde and about 0.5 to 2moles polyalkylene polyamine as disclosed, e.g., in U.S. Pat. Nos.3,442,808; 3,649,229 and 3,798,165 (the disclosures which are herebyincorporated by reference in their entirety). Such Mannich condensationproducts may include a long chain, high molecular weight hydrocarbon onthe phenol group or may be reacted with a compound containing such ahydrocarbon, e.g., polyalkenyl succinic anhydride as shown in saidaforementioned U.S. Pat. No. 3,442,808.

DETERGENTS

Metal-containing rust inhibitors and/or detergents are frequently usedwith ashless dispersants. Such detergents and rust inhibitors includethe metal salts of sulfonic acids, alkyl phenols, sulphurized alkylphenols, alkyl salicylates, napthenates, and other oil solublemono-di-carboxylic acids. Highly basic (or "overbased") metal salts,which are frequently used as detergents, appear particularly prone tointeraction with the ashless dispersant. Usually these metal-containingrust inhibitors and detergents are used in lubricating oil in amounts ofabout 0.01 to 10, e.g., 0.1 to 5, weight percent, based on the weight ofthe total lubricating composition. Highly basic alkaline earth metalsulfonates are frequently used as detergents. They are usually producedby heating a mixture comprising an oil-soluble sulfonate or alkarylsulfonic acid, with an excess of alkaline earth metal compound abovethat required for complete neutralization of any sulfonic acid presentand thereafter forming a dispersed carbonate complex by reacting theexcess metal with carbon dioxide to provide the desired overbasing. Thesulfonic acids are typically obtained by the sulfonation of alkylsubstituted aromatic hydrocarbons such as those obtained from thefractionation of petroleum by distillation and/or extraction or by thealkylation of aromatic hydrocarbons as for example those obtained byalkylating benzene, toluene, xylene, naphthalene, diphenyl and thehalogen derivatives such as chlorobenzene, chlorotoluene andchloronapthalene. The alkylation may be carried out in the presence of acatalyst with alkylating agents having from about 3 to more than 30carbon atoms. For example, haloparaffins, olefins obtained bydehydrogenation of paraffins, polyolefin polymers produced fromethylene, propylene, etc are all suitable. The alkaryl sulfonatesusually contain from about 9 to about 70 or more carbon atoms,preferably from about 16 to about 50 carbon atoms per alkyl substitutedaromatic moiety.

The alkaline earth metal compounds which may be used in neutralizingthese alkaryl sulfonic acids to provide the sulfonates includes theoxides and hydroxides, alkoxides, carbonates, carboxylate, sulfide,hydrosulfide, nitrate, borates and ethers of magnesium, calcium,strontium and barium. Examples are calcium oxide, calcium hydroxide,magnesium oxide, magnesium acetate and magnesium borate. As noted, thealkaline earth metal compound is used in excess of that required tocomplete neutralization of the alkaryl sulfonic acids. Generally, theamount ranges from about 100 to 220 percent, although it is preferred touse at least 125 percent, of the stoichiometric amount of metal requiredfor complete neutralization.

Various other preparations of basic alkaline earth metal alkarylsulfonates are known, such as U.S. Pat. Nos. 3,150,088 and 3,150,089wherein overbasing is accomplished by hydrolysis of analkoxide-carbonate complex with the alkaryl sulfonate in a hydrocarbonsolvent-diluent oil.

A preferred alkaline earth sulfonate additive is magnesium alkylaromatic sulfonate having a high total base number ("TBN") ranging fromabout 300 to about 400 with the magnesium sulfonate content ranging fromabout 25 to about 32 weight percent, based upon the total weight of theadditive system dispersed in mineral lubricating oil.

Neutral metal sulfonates are frequently used as rust inhibitors.Polyvalent metal alkyl salicylate and napthenate materials are knownadditives for lubricating oil compositions to improve their hightemperature performance and to counteract deposition of carbonaceousmatter on pistons (U.S. Pat. No. 2,744,069). An increase in reservebasicity of the polyvalent metal alkyl salicylates and napthenates canbe realized by utilizing alkaline earth metal, e.g., calcium, salts ofmixtures of C₈ -C₂₆ alkyl salicylates and phenates (see U.S. Pat.2,744,069) or polyvalent metal salts of alkyl salicyclic acids, saidacids obtained from the alkylation of phenols followed by phenation,carboxylation and hydrolysis (U.S. Pat. No. 3,704,315) which could thenbe converted into highly basic salts by techniques generally known andused for such conversion. The reserve basicity of these metal-containingrust inhibitors is usefully at TBN levels of between 60 and 150.Included with the useful polyvalent metal salicylate and naphthenatematerials are the methylene and sulfur bridge materials which arereadily derived form alkyl substituted salicylic or naphthenic acids ormixtures of either of both with alkyl substituted phenols. Basicsulfurized salicylates and a method for their preparation is shown inU.S. Pat. No. 3,595,719. Such materials include alkaline earth metal,particularly magnesium, calcium, strontium and barium salts of aromaticacids having the general formula:

    HOOC--ArR'--Xy(ArR'OH).sub.n

where Ar is an aryl radical of 1 to 6 rings, R' is an alkyl group havingfrom about 8 to 50 carbon atoms, preferably 12 to 30 carbon atoms(optimumally about 12), X is a sulfur (--S--) or methylene (--CH₂ --)bridge, y is a number from 0 to 4 and n is a number from 0 to 4.

Preparation of the overbased methylene bridged salicylate-phenate saltis readily carried out by conventional techniques such as by alkylationof a phenol followed by phenation, carboxylation, hydrolysis, methylenebridging a coupling agent such as an alkylene dihalide followed by saltformation concurrent with carbonation. An overbased calcium salt of amethylene bridged phenol-salicylic acid of the general formula:##STR56## with a TBN of 60 to 150 is highly useful in this invention.

The sulfurized phenates can be considered the "metal salt of a phenolsulfide" which thus refers to a metal salt whether neutral or basic, ofa compound typified by the general formula: ##STR57## where x=1 or 2;n=0, 1 to 2 or a polymeric form of such a compound, where R is an alkylradical, n and x are each integers from 1 to 4, and the average numberof carbon atoms in all of the R groups is at least obout 9 in order toensure adequate solubility in oil. The individual R groups may eachcontain from 5 to 40, preferably 8 to 20, carbon atoms. The metal saltis prepared by reacting an alkyl phenol sulfide with a sufficientquantity of metal containing material to impart the desired alkalinityto the sulfurized metal phenate.

Regardless of the manner in which they are prepared, the sulfurizedalkyl phenols generally contain from about 2 to about 14 percent byweight, preferably about 4 to about 12 weight percent sulfur based onthe weight of sulfurized alkyl phenol.

The sulfurized alkyl phenol may be converted by reaction with a metalcontaining material including oxides, hydroxides and complexes in anamount sufficient to neutralize said phenol and, if desired, to overbasethe product to a desired alkalinity by procedures well known in the art.Preferred is a process of neutralization utilizing a solution of metalin a glycol ether.

The neutral or normal sulfurized metal phenates are those in which theratio of metal to phenol nucleus is about 1:2. The "overbased" or"basic" sulfurized metal phenates are sulfurized metal phenates whereinthe ratio of metal to phenol is greater than that of stoichiometric,e.g., basic sulfurized metal dodecyl phenate has a metal content up to(or greater) than 100 percent in excess of the metal present in thecorresponding normal sulfurized metal phenates. The excess metal isproduced in oil-soluble or dispersible form (as by reaction with CO₂).

ANTIWEAR ADDITIVES

Dihydrocarbyl dithiophosphate metal salts are frequently added tolubricating oil compositions as antiwear agents. They may provideantioxidant activity. The zinc salts are most commonly used inlubricating oil in amounts of 0.1 to 10, preferably 0.2 to 2 weightpercent, based upon the total weight of the lubricating oil composition.They may be prepared in accordance with known techniques by firstforming a dithiophosphoric acid, usually by reaction of an alcohol or aphenol with P₂ S₅ and then neutralizing the dithiophosphoric acid with asuitable zine compound.

Mixtures of alcohols may be used including mixtures of primary andsecondary alcohols, secondary generally for importing improved antiwearproperties, with primary giving improved thermal stability properties.Mixtures of the two are particularly useful. In general, any basic orneutral zinc compound could be used but the oxides, hydroxides andcarbonates are most generally employed. Commercial additives frequentlycontain an excess of zinc due to use of an excess of the basic zinccompound in the neutralization reaction.

The zinc dihydrocarbyl dithiophosphates useful in the present inventionare oil soluble salts of dihydrocarbyl esters of dithiophosphoric acidsand may be represented by the following formula: ##STR58## wherein R andR' may be the same or different and are hydrocarbly radicals containingfrom 1 to 18, perferably 2 to 12 carbon atoms and including radicalssuch as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphaticradicals. Particularly preferred as R and R' groups are alkyl groups of2 to 8 carbon atoms. Thus, the radicals may, for example, be ethyl,n-propyl, i-propyl, n-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl,decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butyl-phenyl,cyclohexyl, methlcylcopentyl, propenyl, butenyl, etc. In order to obtainoil solubility, the total number of carbon atoms (i.e., R and R') in thedithiophosphoric acid generally should be about 5 or greater.

ANTIOXIDANTS

Materials which have been observed to be effective antioxidants inlubricating oil compositions are oil-soluble copper compounds, desirablyin the form of synthetic or natural carboxylic acid Cu salts. Examplesinclude C₁₀ to C₁₈ fatty acids such as stearic or palmitic acid. Butunsaturated acids (such as oleic acid), branched carboxylic acids (suchas naphthenic acids) of molecular weight from 200 to 500 and, syntheticcarboxylic acids are all used because of the acceptable handling andsolubility properties of the resulting copper carboxylates.

Suitable oil soluble dithiocarbamates have the general formula (R₁₁ R₁₂N C SS)_(n) Cu ; where n is 1 to 2 and R₁₁ and R₁₂ may be the same ordifferent and are hydrocarbyl radicals containing from 1 to 18 carbonatoms and including radicals such as alkyl, alkenyl, aryl, aralkyl,alkaryl and cycloaliphatic radicals. Particularly preferred as R₁₁ andR₁₂ groups are alkyl groups of 2 to 8 carbon atoms. Thus, the radicalsmay, for example, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl,sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octa-decyl,2-ethylhexyl, phenyl butyl-phenyl, cyclohexyl, methylcyclopentyl,propenyl, butenyl, etc. In order to obtain oil solubility, the totalnumber of carbon atoms (i.e., R₁₁ and R₁₂) generally should be about 5or geater.

Copper sulphonates, phenates, and acetyl acetonates may also be used.

These antioxidants are used in amounts such that, in the finallubricating or fuel composition, a copper concentration of from 1 toabout 500 ppm is present.

Lubricant Oil Basestock

The ashless dispersant, metal detergent, antiwear agent andcompatibilizing material of the present invention will be generally usedin admixture with a lube oil basestock, comprising an oil of lubricatingviscosity, including natural and synthetic lubricating oils and mixturesthereof. The lubricating oil base stock conveniently has a viscosity oftypically about 2.5 to about 12, and preferably about 2.5 to about 9 cs.at 100° C.

Natural oils include animal oils and vegetable oils (e.g., castor, lardoil) liquid petroleum oils and hydrorefined, solvent-treated oracid-treated mineral lubricating oils of the paraffinic, naphthenic andmixed paraffinic-naphthenic types. Oils of lubricating viscosity derivedfrom coal or shale are also useful base oils.

Synthetic lubricating oils include hydrocarbon oils and halo-substitutedhydrocarbon oils such as polymerized and interpolymerized olefins (e.g.,polybutylenes, polypropylenes, propylene-isobutylene copolymers,chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes),poly(1-decenes)); alkylbenzenes (e.g., dodecylbenzenes,tetradecylbenzenes, dinonylbenzenes, di(2-ethylhxyl)benzenes);polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); andalkylated diphenyl ethers and alkylated diphenyl sulfides and thederivatives, analogs and homologs thereof.

Alkylene oxide polymers and interpolymers and derivatives thereof wherethe terminal hydroxly groups have been modified by esterification,etherification, etc., constitute another class of known syntheticlubricating oils. These are exemplified by polyoxyalkylene polymersprepared by polymerization of ethylene oxide or propylene oxide, thealkyl and aryl ethers of these polyoxyalkylene polymers (e.g.,methyl-polyisopropylene glycol ether having an average molecular weightof 1000, diphenyl ether of poly-ethylene glycol having a molecularweight of 500-1000, diethyl ether of polypropylene glycol having amolecular weight of 1000-1500); and mono- and polycarboxylic estersthereof, for example, the acetic acid esters, mixed C₃ -C₈ fatty acidesters and C₁₃ 0xo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises theesters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acids and alkenyl succinic acids, maleic acid, azelaic acid,suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic aciddimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with avariety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecylalcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycolmonoether, propylene glycol). Specific examples of these esters includedibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctylsebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate,didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester oflinoleic acid dimer, and the complex ester formed by reacting one moleof sebacic acid with two moles of tetraethylene glycol and two moles of2-ethylhexanoic acid.

Esters useful as synthetic oils also include those made from C₅ to C₁₂monocarboxylic acids and polyols and polyol ethers such as neopentylglycol, trimethylolpropane, pentaerythritol, dipentaerythritol andtripentaerythritol.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, orpolyaryloxysiloxne oils and silicate oils comprise another useful classof synthetic lubricants; they include tetraethyl silicate,tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate,tetra-(4-methyl-2-ethylhexyl)silicate,tetra-(p-tert-butyl-phenyl)silicate,hexa-(4-methyl-2-pentoxy)disiloxane, poly(methyl)siloxanes andpoly(methylphenyl)siloxanes. Other synthetic lubricating oils includeliquid esters of phosphorus-containing acids (e.g., tricresyl phosphate,trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymerictetrahydrofurans.

Unrefined, refined and rerefined oils can be used in the lubricants ofthe present invention. Unrefined oils are those obtained directly from anatural or synthetic source without further purification treatment. Forexample, a shale oil obtained directly from retorting operations, apetroleum oil obtained directly from distillation or ester oil obtaineddirectly from an esterification process and used without furthertreatment would be an unrefined oil. Refined oils are similar to theunrefined oils except they have been further treated in one or morepurification steps to improve one or more properties. Many suchpurification techniques, such as distillation, solvent extraction, acidor base extraction, filtration and percolation are known to theoseskilled in the art. Rerefined oils are obtained by processes similar tothose used to obtain refined oils applied to refined oils which havebeen already used in service. Such rerefined oils are also known asreclaimed or reprocessed oils and often are additionally processed bytechniques for removal of spent additives and oil breakdown products.

This invention is further illustrated by the examples which follow. Theexamples are not intended to limit the scope of the invention in anyway.

EXAMPLES PREPARATION OF DISPERSANTS USING 1300 M_(n) PIB Example 1(a)

200 g of a polyisobutenyl succinic anhydride (PIBSA) having asaponification number (SAP) of 90.4 and active ingredient level (A.I.)of 90.5 wt. % and a number average molecular weight of 1300 were mixedin a reaction flask with 176 g of S150N lubricating oil (solvent neutralhaving a viscosity of about 150 SSU at 100° C.) and heated to about 149°C. Then, 16.7 g of a commercial grade of polyethyleneamine known aspolyamine bottoms (PAM) was added and the mixture heated to 150° C. forabout 2 hours, this was followed by a half hour of nitrogen stripping.The oil solution was filtered. It analyzed for 1.46 wt. % nitrogen andhad a kinematic viscosity (kv) of 225 cSt at 100° C.

Example 1(b)

The Example 1(b) material was prepared in the same manner as Example1(a) except that after nitrogen stripping, the reaction mixture wascooled to 100° C. and 33.8 g of ethyl acetoacetate was added. Thereaction mixture was maintained at 100° C. for one hour and heated to150° C. for another 2 hours, followed by a half hour of nitrogenstripping at 150° C. It was filtered and collected. It analyzed for 1.37wt. % N and had a kv of 331 cSt at 100° C.

Example 1(c)

About 16.7 g (0.087 mole) of PAM was mixed with 33.8 g (0.26 mole) ofethylacetoacetate and heated to 100° C. for one hour. Thereafter thereaction mixture was heated to 150° C. for two hours and nitrogenstripped to remove the ethanol by-product. The adduct was cooled toabout 100° C. and an oil solution containing 200 g of the PIBSA used inExample 1(a) and 203 g of mineral oil S15ON was added. The reactionmixture was then heated to 150° C. and soaked at this temperature for 2hours followed by nitrogen stripping for one hour. The filtered oilsolution analyzed for 1.36 wt. % nitrogen and had a kv of 419 cSt at100° C.

PREPARATION OF DISPERSANTS USING 1700 M_(n) PIB Example 2(a)

200 g (0.1238 mole) of a PIBSA having a SAP number of 69.3 an A.I. of85.2 and a number average molecular weight of 1700 were mixed in areaction flask with 151 g of S15ON oil while stirring under a nitrogenblanket. Then 12.6 g (0.0651 mole) of PAM was added and the reactionmixture was slowly heated to 150° C. for 2 hours, and then nitrogenstripped for a half hour at 150° C. The oil solution was filtered andanalyzed for 1.17 wt. % nitrogen and had a kv of 416 cSt at 100° C.

Example 2(b)

Example 2(b) was prepared in the same manner as example 2(a) except thatafter the nitrogen stripping was concluded, 25.4 g (0.195 mole) of ethylacetoacetate was added at 100° C. The reaction mixture was kept at 100°C. for one hour, heated to 150° C. for two hours, and nitrogen strippeda one half hour. The filtered oil solution analyzed for 1.11 wt. %nitrogen and had a kv of 563 cSt at 100° C.

Example 2(c)

About 288 g (0.651 mole) of a polyamine-ethyl acetoacetate adductprepared as described in Example 1(c) was mixed with 200 g (0.1238 mole)of the PIBSA used in Example 2(a) and 168 g of S15ON oil. The reactionmixture was then slowly heated to 150° C. (under nitrogen) for 2 hours.The oil solution was then nitrogen stripped for a half hour andfiltered. The product analyzed for 1.18 wt. % nitrogen and had a kv of742 cSt at 100° C.

PREPARATION OF DISPERSANTS USING 1900 M_(n) PIB Example 3(a)

200 g (0.1063 mole) of a PIBSA having a SAP number of 59.2 and an A.I.of 78.9 wt. % with a number average molecular weight of 1900 were mixedin a reaction flask with 138 g of S15ON oil and 10.8 g (0.0559 mole) ofPAM. The reaction mixture was then slowly heated to 150° C. and soakedfor two hours. The oil solution was sparged with nitrogen for one halfhour and filtered. It analyzed for 1.05 wt. % nitrogen and had a kv of504 cSt at 100° C.

Example 3(b)

The material of Example 3(b) was prepared in the same manner as Example3(a) except that after the nitrogen stripping, the reaction mixture wascooled to 100° C. and 21.8 g (0.1677 mole) of ethyl acetoacetate wasadded. The oil solution was heated to 150° C. for two hours and strippedwith nitrogen for a half hour. The filtered product analyzed for 0.99wt. % nitrogen and had a kv of 800 cSt at 100° C.

Example 3(c)

About 24.7 g (0.0559 mole) of a polyamine ethyl acetoacetate reactionproduct prepared as described in Example 1(c) was mixed with 200 g(0.1063 mole) of the PIBSA used in Example 3(a)-3(c) and 151.4 g ofS15ON oil. The reaction mixture was then slowly heated to 150° C. andheld at this temperature for two hours. The oil solution was thennitrogen stripped for a half hour at 150° C. and filtered. The filteredproduct analyzed for 0.99 wt. % nitrogen and had a kv of 974 cSt at 100°C.

PREPARATION OF DISPERSANTS USING 2250 M_(n) PIB Example 4(a)

About 200 g (0.09 mole) of a PIBSA having a SAP number of 52.2 and anA.I. of 78.9 wt. % with a number average molecular weight of 2250 werecombined with 9.5 g (0.05 mole) of PAM, and 123.5 g of S15ON oil andslowly heated to 150° C. The reaction mixture was heat soaked at 150° C.for two hours and nitrogen stripped for a half hour. The filtered oilsolution analyzed for 0.95 wt. % nitrogen and had a kv of 671 cSt at100° C.

Example 4(b)

The material of Example 4(b) was prepared in the same manner as Example4(a) except that after the nitrogen stripping, the reaction product wascooled to 100° C. and 19.5 (0.15 mole) of ethyl acetoacetate was added.The mixture was kept at 100° C. for one hour and heated to 150° C. fortwo hours. It was stripped with nitrogen for a half hour at 150° C. toremove the ethanol by-product and filtered. It analyzed for 0.91 wt. %nitrogen and had a kv of 926 cSt at 150° C.

Example 4(c)

About 22.2 g (0.05 mole) of the PAM ethyl acetoacetate reaction productprepared as described in Example 1(c) was mixed with 200 g (0.09 mole)of the PIBSA used in Example 4(a) and 136 g of S15ON oil. The reactionmixture was then slowly heated to 150° C. for two hours and nitrogenstripped for one half hour. The filtered product analyzed for 0.95 wt. %nitrogen and had a kv of 1057 cSt at 100° C.

The materials of Examples 1(a) to 4(c) were mixed with various amountsof mineral oil. The resulting formulations were tested in using variousstandard procedures including the sludge inhibition test (SIB) and thevarnish inhibition test (VIB).

The SIB and VIB tests forecast the performance of a lubricant in agasoline engine.

The SIB test employs a used crankcase mineral lubricating oilcomposition (having an original viscosity of about 325 SUS at 37.8° C.)which has been used in a taxicab driven generally only for short trips.This causes a buildup of sludge precursors. The oil used contains only arefined base mineral oil, a viscosity index improver, a pour pointdepressant and zinc dialkyldithiophosphate antiwear additives. The oilcontains no sludge dispersants. Such oil is acquired by draining andrefilling taxicab crankcases at about 1000-2000 mile intervals.

The SIB test is conducted in the following manner: the used crankcaseoil is freed of sludge by centrifuging for one half hour at about 39,000gravities (gs). The resulting clear bright red oil is then decanted fromthe separated insoluble particles. However, the supernatant oil stillcontains oil-soluble sludge precursors which (under the conditionsemployed by the SIB test) tend to form additional oil-insoluble depositsof sludge. The sludge inhibiting properties of the additive being testedis determined by adding to the used oil, 0.5 wt. % on an active basis,of the particular additive being tested. Ten grams of the sample testedis then placed in a stainless steel centrifuge tube and heated at 140°C. for 16 hours in the presence of air. Following the heating, the tubecontaining oil is cooled and centrifuged for 30 minutes at about 39,000gs. Any deposits of new sludge that form in this step are separated fromthe decanting supernatant oil and then carefully washed with 15 ml. ofpentane to remove all remaining oils. The weight of the new solid sludgethat forms in the test in milligrams) is determined (after drying theresidue) by weighing it. The results are reported as milligrams ofsludge per ten grams of oil. Differences as small as one part per tenthousand can be measured. The less new sludge formed, obviously the moreeffective is the additive as a dispersant. In other words, if theadditive is effective, it will maintain in suspension, duringcentrifugation, a portion of the new sludge that forms on heating andoxidation.

In the VIB test, a test sample consisting of ten grams of lubricatingoil containing 0.5 wt. %, (on an active basis) of the additive beingevaluated is used. The test oil is a lubricating oil obtained from ataxi which has been operated for about 2000 miles with the lubricatingoil. The sample is heat soaked overnight at about 140° C. and thereaftercentrifuged to remove the sludge. The supernatant fluid is subjected toheat cycling from about 150° C. to room temperature over a period of 3.5hours at a frequency of about two cycles per minute. During the heatingphase, a gas containing a mixture of 0.7 volume percent SO₂, 1.4 volumepercent NO and the balance air is bubbled through the test sample;during the cooling phase, water vapor is bubbled through the sample. Atthe end of the test period, (which testing cycle can be repeated asnecessary to determine the inhibiting effect of any additive), the wallsurfaces of the test flasks in which the samples are visually evaluatedfor varnish inhibition. The amount of varnish deposited on the walls israted at values of from one to eleven with the higher number being thegreater amount of varnish. This test also forecasts the varnish resultsobtained as a consequence of carrying out the ASTM MS-VD engine tests.

Table II portrays all of the results from these Examples 1(a) to 4(c).

                                      TABLE II                                    __________________________________________________________________________                   PIBSA SAP                                                                            PIBSA PIBSA, g.                                                                           PAM, g.                                                                            EAA, g.   wt. %                        Example   PIB --M.sub.n                                                                      NO. (1)                                                                              (wt. % AI)                                                                          (moles)                                                                             (moles)                                                                            (moles)                                                                            OIL, g.                                                                            N   Vis                                                                               SIB                                                                              VIB               __________________________________________________________________________    1(a) [Comparative]                                                                      1300 90.4   90.5  200 g 16.7 g                                                                             --   176  1.46                                                                              225 3.95                                                                             4                                             (.16) (.087)                                      1(b)      1300 90.4   90.5  200 g 16.7 g                                                                             33.8 g                                                                             203  1.37                                                                              331 1.35                                                                             3                                             (.16) (.087)                                                                             (.26)                                  1(c)      1300 90.4   90.5  200 g (3)  (3)  203  1.36                                                                              419 2.19                                                                             3                                             (.16)                                             2(a) [Comparative]                                                                      1700 69.3   85.2  200 g 12.6 g                                                                             --   151  1.17                                                                              4.16                                                                              3.95                                                                             5                                             (.123)                                                                              (.065)                                      2(b)      1700 69.3   85.2  200 g 12.6 g                                                                             25.4 g                                                                             168  1.11                                                                              563 2.03                                                                              31/2                                         (.123)                                                                              (.065)                                                                             (.195)                                 2(c)      1700 69.3   85.2  200 g (4)  (4)  168  1.18                                                                              742 2.27                                                                             4                                             (.123)                                            3(a) [Comparative]                                                                      1900 59.6   82.2  200 g 10.8 g                                                                             --   138  1.05                                                                              504 3.43                                                                             5                                             (.106)                                                                              (.05)                                       3(b)      1900 59.5   82.2  200 g 10.8 g                                                                             21.8 g                                                                             151   .99                                                                              800 2.15                                                                             4                                             (.106)                                                                              (.056)                                                                             (.164)                                 3(c)      1900 59.5   82.2  200 g (5)  (5)  151   .99                                                                              974 1.63                                                                             4                                             (.106)                                            4(a) [Comparative]                                                                      2250 52.2   78.9  200 g 9.5 g                                                                              --     123.5                                                                             .95                                                                              671 2.34                                                                              31/4                                         (.09) (.05)                                       4(b)      2250 52.2   78.9  200 g 9.5 g                                                                              19.5 g                                                                             136   .91                                                                              926 1.74                                                                              31/4                                         (.09) (.05)                                                                              (.15)                                  4(c)      2250 52.2   78.9  200 g (6)  (6)  136   .95                                                                              1057                                                                              1.69                                                                              31/2                                         (.09)                                             __________________________________________________________________________     Notes to Table II:                                                            (1) Saponification No. = mgs. KOH required to saponify 1 gram of sample       (2) Viscosity units = cSt at 100° C.                                   (3) Prereacted PAMEAA, 38.7 g (0.087 mole)                                    (4) Prereacted PAMEAA, 28.8 g (0.065 mole)                                    (5) Prereacted PAMEAA, 24.7 g (0.056 mole)                                    (6) Prereacted PAMEAA, 22.15 g (0.050 mole)                              

For each set of materials using a single molecular weight PIB startingmaterial, it is clear that the SIB results for the inventivecompositions are substantially superior to those for the comparativeexample. A similar trend is apparent for the VIB tests although for the2250 M_(n) materials of Examples 4(b) and 4(c), the VIB tests giveessentially the same results as the material of comparative Example4(a).

Even on preliminary tests such as these, the inventive compositions showclear superiority over their closest relations, the materials containedthe non-adducted PIBSA-PAM.

The same set of dispersants were then mixed into lubricating oilformulations and the viscosity measured at 100° C. and -20° C.

They were mixed with Solvent 150 LP and 0.2 wt. % pour depressant atdispersant levels of 5 wt. % and 10 wt. %. The noted viscositymeasurements were then taken. The results are shown in Table III. Theunits of viscosity are centipoise.

                  TABLE III                                                       ______________________________________                                        VISCOSITIES                                                                          5 wt. % dispersant*                                                                         10 wt. % dispersant*                                     Dispersant                                                                             PIB     KV      CCS   PIB   KV    CCS                                (Ex. No.)                                                                              (--M.sub.n)                                                                           (cP)    (cP)  (--M.sub.n)                                                                         (cP)  (cP)                               ______________________________________                                        1(a)     1,300   6.14    2,966 1,300 7.18  4.047                              1(b)     1,300   6.09    2,867 1,300 7.18  3,730                              2(a)     1,700   6.42    3,116 1,700 7.89  4,572                              2(b)     1,700   6.42    3,014 1,700 7.96  4,254                              3(a)     1,900   6.53    3,170 1,900 7.92  4,551                              3(b)     1,900   6.47    3,022 1,900 8.10  4,356                              4(a)     2,250   6.64    3,245 2,250 8.49  4,901                              4(b)     2,250   6.58    3,116 2,250 8.59  4,638                              ______________________________________                                         *The dispersants were mixed with S150N lubricating oil and 0.2 wt. % of a     commercial pour point depressant.                                        

In each case, it is clear that the inventive material causes no loss ofviscosity at the higher temperatures. Moreover, a substantial benefit isgained at lower temperatures through the use of these materials.

Finally, the dispersants of this invention were mixed in standard 10W30and 5W30 motor oil formulations.

                  TABLE IV                                                        ______________________________________                                                     VISCOSITY (cP)                                                                10W30 Form.                                                                              5W30 Form.                                            Dispersant     100° C.                                                                        -20° C.                                                                         100° C.                                                                      -20° C.                          ______________________________________                                        Ex. 4(a) Comparative                                                                         10.42   3400     10.46 3653                                    Ex. 4(b)       10.31   3209     10.52 3436                                    Ex. 4(c)       10.46   3296     10.56 3505                                    ______________________________________                                    

The invention has been described by specific disclosure and by examples.It will be apparent to those skilled in the art that various changes andmodifications to the claimed invention may be made which fall into thescope of equivalents.

We claim as our invention:
 1. An oleaginous composition comprising:alubricating oil, and a dispersant effective amount of an adduct of theformula: ##STR59## wherein Z¹ and Z³ are the same or different and aremoieties of the formula: ##STR60## Z² is a moiety of the formula:##STR61## wherein R², R³ and R⁴ are the same or different and arealkylene of from 1 to 6 carbon atoms, m is an integer of from 1 to 5,each A' is independently selected from the group consisting of H, A andthe moiety: ##STR62## wherein A" is H or A, R³ is as defined above, R⁶is alkylene of from 1 to 6 carbon atoms, T¹ and T² are the same ordifferent and each comprises a member selected from the group consistingof moities of the formula: ##STR63## wherein B' is substituted orunsubstituted alkyl or aryl-containing group, n¹ is an integer of 0 to10, n² is an integer of 0 to 10, n³ is an integer of from 0 to 10, n⁴ isan integer of from 0 to 10, with the provisos that the sum of n¹, n², n³and n⁴ is from 3 to 10 and the sum of n¹, n³ and n⁴ is at least 1,wherein R¹ and R⁵ are independently an olefin polymer having a numberaverage molecular weight (M_(n)) between about 650 and 3,500, andwherein A comprises a tautomeric substituent of the formula: ##STR64##wherein R¹⁰ is substituted or unsubstituted alkyl or aryl containinggroups, with the proviso that at least one of the A' or A" groupscomprises said tautomeric substituent, wherein at least about 95% of T¹and T² groups in said adduct dispersant comprise said succinimide moietyof the formula: ##STR65## wherein R⁵ is as defined above.
 2. Thecomposition of claim 1 wherein R¹ and R₃ are polyisobutylene.
 3. Thecomposition of claim 2 wherein the polyisobutylene has a M_(n) betweenabout 800 and about
 3000. 4. The composition of claim 3 wherein thepolyisobutylene has a M_(n) between about 900 and about
 2300. 5. Thecomposition of claim 2 wherein R², R⁴ and R⁶ are alkylene of from 2 to 4carbon atoms.
 6. The composition of claim 5 wherein R², R⁴ and R⁶ are--CH₂ CH₂ --.
 7. The composition of claim 2 wherein n² is zero and thesum of n¹, n³ and n⁴ is from 3 to
 7. 8. The composition of claim 6wherein n² is zero and the sum of n¹, n³ and n⁴ is from 3 to
 7. 9. Thecomposition of claim 1 wherein R¹⁰ is a methyl group.
 10. Thecomposition of claim 2 wherein R¹⁰ is a methyl group.
 11. Thecomposition of claim 6 wherein R¹⁰ is a methyl group.
 12. Thecomposition of claim 8 wherein R¹⁰ is a methyl group.
 13. Thecomposition of claim 1 also containing an overbased alkaline earth metalsulfonate detergent material, an overbased alkaline earth metal phenatedetergent material or a mixture thereof.
 14. The composition of claim 13wherein the alkaline earth metal is calcium.
 15. The composition ofclaim 13 wherein the alkaline earth metal is magnesium.
 16. Thecomposition of claim 1 wherein said lubricating oil is present in amajor amount.
 17. The composition of claim 2 wherein said lubricatingoil is present in a major amount.
 18. The composition of claim 1 alsocontaining a friction modifier material.
 19. An oleaginous compositioncomprising:a lubricating oil; a detergent material; and a dispersanteffective amount of mixtures of adducts having the formulae: ##STR66##wherein Z¹ and Z³ are the same or different and are moities of theformula: ##STR67## Z² is a moiety of the formula: ##STR68## wherein R²,R³ and R⁴ are the same or different and are alkylene of from 1 to 6carbon atoms, m is an integer of from 1 to 5, each A' is independentlyselected from the group consisting of H, A and the moiety: ##STR69##wherein A" is H or A, R³ is as defined above, R⁶ is alkylene of from 1to 6 carbon atoms, T¹ and T² are the same or different and eachcomprises a member selected from the group consisting of moities of theformula: ##STR70## wherein B' is substituted or unsubstituted alkyl oraryl-containing group, n¹ is an integer of 0 to 10, n² is an integer of0 to 10, n³ is an integer of from 0 to 10, n⁴ is an integer of from 0 to10, with the provisos that the sum of n¹, n², n³ and n⁴ is from 3 to 10and the sum of n¹, n³ and n⁴ is at least 1, wherein R¹ and R⁵ areindependently an olefin polymer having a number average molecular weight(M_(n)) between about 650 and 3,500, and wherein A comprises atautomeric substituent of the formula: ##STR71## wherein R¹⁰ issubstituted or unsubstituted alkyl or aryl containing groups, with theproviso that at least one of the A' or A" groups comprises saidtautomeric substituent, wherein at least about 95% of T¹ and T² groupsin adduct dispersants comprise said succinimide moiety of the formula:##STR72## wherein R⁵ is as defined above.
 20. The composition of claim19 also containing a zinc dihydrocarbyl dithiophosphate in an antiweareffective amount.
 21. The composition of claim 20 wherein R¹ and R⁵ arepolyisobutylene.
 22. The composition of claim 21 wherein thepolyisobutylene has a M_(n) between about 800 and about
 3000. 23. Thecomposition of claim 22 wherein the polyisobutylene has a M_(n) betweenabout 900 and about
 2300. 24. The composition of claim 21 wherein R², R⁴and R⁶ are alkylene of from 2 to 4 carbon atoms.
 25. The composition ofclaim 24 wherein R², R⁴ and R⁶ are --CH₂ CH₂ --.
 26. The composition ofclaim 22 wherein n² is zero and the sum of n¹, n³ and n⁴ is from 3 to 7.27. The composition of claim 21 wherein n² is zero and the sum of n¹, n³and n⁴ is from 3 to
 7. 28. The composition of claim 20 wherein R¹⁰ is amethyl group.
 29. The composition of claim 21 wherein R¹⁰ is a methylgroup.
 30. The composition of claim 25 wherein R¹⁰ is a methyl group.31. The composition of claim 27 wherein R¹⁰ is a methyl group.
 32. Thecomposition of claim 20 wherein the detergent material is an overbasedalkaline earth metal sulfonate, an overbased alkaline earth metalphenate or a mixture thereof.
 33. The composition of claim 32 whereinthe alkaline earth metal is calcium.
 34. The composition of claim 32wherein the alkaline earth metal is magnesium.
 35. The composition ofclaim 20 wherein said lubricating oil is present in a major amount. 36.The composition of claim 21 wherein said lubricating oil is present in amajor amount.
 37. The composition of claim 20 also containing a frictionmodifier material.